Process and chemistry of plating of through silicon vias

ABSTRACT

A method and apparatus for processing a silicon substrate are provided. In some implementations, the method comprises providing a silicon substrate having an aperture containing an exposed silicon contact surface at a bottom of the aperture, depositing a metal seed layer on the exposed silicon contact surface and exposing the silicon substrate to an electroplating process by flowing a current through a backside of the silicon substrate to form a metal layer on the metal seed layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of U.S. Provisional Patent Application Ser. No. 62/281,470, filed Jan. 21, 2016, which is herein incorporated by reference in its entirety.

BACKGROUND

Field

Implementations of the present disclosure generally relate to methods for depositing materials on substrates, and more specifically to methods for filling features having high aspect ratios.

Description of the Related Art

Multilevel, 45 nm node metallization is one of the key technologies for the next generation of very large scale integration (VLSI). The multilevel interconnects that lie at the heart of this technology possess high aspect ratio features, including contacts, vias, lines, and other apertures. Reliable formation of these features is significant for the success of VLSI and the continued effort to increase quality and circuit density on individual substrates. Therefore, there is a great amount of ongoing effort being directed to the formation of void-free features having high aspect ratios of 20:1 (height:width) or greater.

Copper and tungsten are choice metals for filling VLSI features, such as a submicron high aspect ratio contacts (HARC) on a substrate. Contacts are formed by depositing a conductive interconnect material, such as copper or tungsten into an aperture (e.g., via) on the surface of an insulating material disposed between two spaced-apart conductive layers. A high aspect ratio of such an opening may inhibit deposition of a conductive interconnect material to fill an aperture. Although copper and tungsten are popular interconnect materials, deposition processes for depositing these materials may suffer by forming a void or a seam within the contact plug.

Therefore, a need exists for a method to fill a feature with a conductive contact material, such that the contact material is deposited free of voids, seams, and other defects.

SUMMARY

Implementations of the present disclosure generally relate to methods for depositing materials on substrates, and more specifically to methods for filling features having high aspect ratios. In one implementation, a method for depositing a material on a substrate is provided. The method comprises depositing a conformal oxide layer over at least one sidewall and bottom surface of a feature formed in a silicon substrate. The substrate comprises a field region surrounding the feature and a backside, wherein the feature extends from the field region toward the backside. The method further comprises selectively removing a portion of the conformal oxide layer from the bottom surface of the feature to expose a portion of the silicon substrate. The method further comprises depositing a metal seed layer on the exposed portion of the silicon substrate at the bottom of the feature. The method further comprises exposing the silicon substrate to an electroplating process by flowing a current through the backside of the silicon substrate to form a metal layer on the metal seed layer.

In one implementation, the method comprises forming a conformal barrier layer on the oxide layer after depositing the metal seed layer on the exposed silicon substrate at the bottom of the feature.

In one implementation, exposing the substrate to an electroplating process by flowing a current through the backside of the silicon substrate to form a metal layer on the metal seed layer comprises exposing the backside of the substrate to a wet contact solution comprising a hydrofluoric acid solution and exposing the seed layer to a copper containing solution.

In one implementation, the wet contact solution further comprises potassium fluoride.

In one implementation, the barrier layer comprises a titanium nitride (TiN), tungsten nitride (WN), or tungsten-silicon nitride (WSiN). In one implementation, the conformal oxide layer is a silicon dioxide layer.

In one implementation, the metal of the metal seed layer is selected from cobalt and nickel. In one implementation, the metal of the metal seed layer is nickel deposited by an electroless process. In one implementation, the metal of the metal seed layer is cobalt deposited by either an electroless or a chemical vapor deposition process. In one implementation, the metal layer comprises copper.

In one implementation, the feature is an aperture selected from contacts, vias, and lines.

In one implementation, exposing the substrate to an electroplating process by flowing a current through a backside of the substrate to form a metal layer on the metal seed layer comprises exposing the backside of the substrate to a potassium hydroxide solution and exposing the seed layer to a copper containing solution.

In another implementation, a method for depositing a material on a substrate is provided. The method comprises depositing an oxide layer over at least one sidewall and bottom surface of a feature formed in a silicon substrate. The substrate comprises a field region surrounding the feature and having an oxide layer disposed thereon and a backside, wherein the feature extends from the field region toward the backside. The method further comprises selectively removing a portion of the oxide layer from the bottom surface of the feature to expose a portion of the silicon substrate. At least a portion of the oxide layer remains on the at least one sidewall. The method further comprises depositing a metal seed layer on the exposed portion of the silicon substrate at the bottom of the feature. The method further comprises forming a barrier layer on the portion of the oxide layer remaining on the at least one sidewall. The method further comprises exposing the silicon substrate to an electroplating process by flowing a current through the backside of the silicon substrate to form a metal layer on the metal seed layer.

In yet another implementation, a method for depositing a material on a substrate is provided. The method comprises depositing an oxide layer over at least one sidewall and bottom surface of a feature formed in a silicon substrate. The substrate comprises a field region surrounding the feature and having an oxide layer disposed thereon and a backside, wherein the feature extends from the field region toward the backside. The method further comprises selectively removing a portion of the oxide layer from the bottom surface of the feature to expose a portion of the silicon substrate, wherein selectively removing a portion of the conformal oxide layer comprises exposing the conformal oxide layer to an argon-based sputter etching process followed by a wet etch process. At least a portion of the oxide layer remains on the at least one sidewall. The method further comprises depositing a metal seed layer on the exposed portion of the silicon substrate at the bottom of the feature. The method further comprises forming a barrier layer on the portion of the oxide layer remaining on the at least one sidewall. The method further comprises exposing the silicon substrate to an electroplating process by flowing a current through the backside of the silicon substrate to form a metal layer on the metal seed layer.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above-recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to implementations, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical implementations of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective implementations.

FIGS. 1A-1H illustrate schematic cross-sectional views of a through silicon via (TSV) fabrication process according to implementations described herein;

FIG. 2 illustrates a flow chart depicting a deposition process according to implementations described herein;

FIG. 3 illustrates a schematic cross-sectional view of a plating cell that may be used to perform the deposition processes described herein; and

FIG. 4 illustrates another schematic cross-sectional view of a plating cell that may be used to perform the deposition processes described herein.

To facilitate understanding, identical reference numerals have been used, wherever possible, to designate identical elements that are common to the figures. It is contemplated that elements and/or process operations of one implementation may be beneficially incorporated in other implementations without additional recitation.

DETAILED DESCRIPTION

Implementations of the present disclosure generally relate to methods for depositing materials on substrates, and more specifically to methods for filling high aspect ratio features. Implementations described herein are especially advantageous in through-silicon via (TSV) applications. Implementations of the methods described herein are also suitable for plating applications on standard substrates. TSV applications include electrical connections passing completely through a silicon substrate, such as in 3D packages and 3D integrated circuits. TSV applications commonly include multiple integrated circuits disposed on one another. For example, a 3D integrated circuit may include multiple silicon substrates stacked vertically on one another.

Some implementations described herein relate to copper plating of TSVs. Conventional plating processes are insufficient for plating copper in high aspect ratio (e.g., AR ˜20-50) TSVs due to lack of conformality of the as-deposited copper materials. To partially improve copper plating conformality and stimulate bottom-up plating various additives are added typically added to the copper plating chemistry. However, the addition of such additives drastically reduces the plating rate. Therefore, it is desirable to plate with a simple copper containing chemistry with minimum additives in order to maximize the copper plating rate.

In some implementations described herein, methods for bottom-up via plating using wet wafer backside contact are used to achieve conformal copper deposition at high plating rates. In some implementations, a metallic film or silver paste is applied to the backside of the substrate to allow current to flow through the substrate. However, use of silver paste or metallic films adds complexity to the process.

The methods and structures described herein may be performed in individual chambers, respectively coupled to, or part of, an integrated processing tool, such as a cluster tool. Examples of the integrated tools include the CENTURA® and ENDURA® integrated tools, both available from Applied Materials, Inc., of Santa Clara, Calif. In one implementation, the cluster tool may have processing chambers that are configured to perform a number of substrate processing operations such as cyclical layer deposition, chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), etch, pre-clean, degas, anneal, orientation and other substrate processes.

FIGS. 1A-1H illustrate a schematic cross-sectional view of a feature 102 as the various processing operations of a processing sequence 200 (FIG. 2) are performed on a substrate 100. At operation 210, the feature 102 is formed in the substrate 100 as depicted in FIG. 1A. FIG. 1A illustrates a cross-sectional view of the substrate 100 having a field region 105, a backside 106 and the feature 102 formed into a surface of the substrate 100. The feature has an opening 107. The feature 102 is defined by at least one sidewall 108 and a bottom surface 110. In some implementations, the bottom surface 110 is an exposed silicon or silicon-containing surface (e.g., monocrystalline silicon surface). In some implementations, the bottom surface 110 is an exposed germanium or germanium-containing surface. In some implementations, the bottom surface 110 is defined by an exposed surface of the substrate 100.

The feature 102 may include features with high height to width aspect ratios (the ratio of the height of the bare hole divided by the width of the hole) of at least about 5:1 or more (e.g., an aspect ratio of 6:1 or more, 7:1 or more, 8:1 or more, 9:1 or more, 10:1 or more, 11:1 or more, 12:1, 16:1 or more, or about 10:1 to about 20:1, or in the range of about 30:1 to about 50:1; or in the range of about 70:1 to about 100:1). Exemplary feature definitions include vias, trenches, gaps, lines, contact-holes, through-holes or other feature definitions utilized in a semiconductor, solar, or other electronic devices, such as high ratio contact plugs. The feature 102 may include apertures such as contact holes, vias, or trenches. In some implementations where the aperture is a via, the via has a high aspect ratio (e.g., AR ˜20-50).

The feature 102 may be formed using reactive ion etching techniques or other anisotropic etching techniques. In one implementation, plasma or ion beam of etch gas may be directed to the substrate 100 to form the feature 102. The etch gas may include SF₆, C₃F₈ CF₄, BF₃, BI₃, N₂, Ar, PH₃, AsH₃, B₂H₆, H₂, Xe, Kr, Ne, He, SiH₄, SiF₄, GeH₄, GeF₄, CH₄, AsF₅, PF₃, PF₅, or combinations thereof. In one implementation, a sputter etch may be directed to the substrate 100 to form the feature 102. The sputter etch may be performed with an argon plasma. In one implementation, the feature 102 is formed using a plasma implant tool having a voltage bias greater than 8 kV.

The substrate 100 may comprise a semiconductor material such as, for example, silicon, germanium, or silicon germanium. The feature 102 may be formed in the substrate 100 using conventional lithography and etching techniques. In some implementations, the feature 102 may be formed using a pulsed or time-multiplexed etching process, such as the Bosch process.

In some implementations, an oxide layer 112 may be formed on the field region 105 prior to forming the feature 102 as depicted in FIG. 1A. The oxide layer 112 may be a thin oxide layer having a thickness in the range of from about 500 Å and about 1,000 Å. The oxide layer 112 may be an oxide containing silicon layer (e.g., SiO₂, SiO). The oxide layer 112 may be formed on the field region 105 by exposing the substrate 100 to a cleaning process. In some implementations, the optional clean process may comprise exposing the substrate 100 to Standard Clean-1 (“SC-1”) chemistry (e.g., a 1:1:5 solution of NH₄OH (ammonium hydroxide)+H₂O₂ (hydrogen peroxide)+H₂O (water) at 75 or 80 degrees Celsius typically for 10 minutes). The optional pre-clean process may further comprise at least one of exposure to a hydrofluoric acid containing solution and a Standard Clean 2 (“SC-2”) chemistry (e.g., a 1:1:6 solution of HCl+H₂O₂+H₂O at 75 or 80 degrees Celsius). In some implementations, the oxide layer 112 may be formed on the field region 105 using deposition techniques such as chemical vapor deposition (CVD).

At operation 220, an oxide layer 120 is formed on the oxide layer 112, the bottom surface 110 and the at least one sidewall 108 of the feature 102 as depicted in FIG. 1B. The oxide layer 120 may be a conformal oxide layer. The oxide layer 120 may be thicker on the at least one sidewall 108 than on the bottom surface 110. The oxide layer 120 may have a thickness in the range of about 100 Å and about 3,000 Å (e.g., about 500 Å and about 1,000 Å; 1,000 Å and about 2,000 Å; 2,000 Å and about 3,000 Å; 2,500 Å and about 3,000 Å). In one implementation, the portion of the oxide layer 120 on the at least one sidewall 108 is from about 2,000 Å and about 3,000 Å and the portion of the oxide layer 120 on the bottom surface 110 from about 500 Å and about 1,200 Å.

The oxide layer 120 may be an oxide containing silicon layer (e.g., SiO₂, SiO). The oxide layer 120 may be a silicon oxide or a silicon dioxide containing layer. The silicon oxide or silicon dioxide layer may serve as an insulating layer. The silicon oxide or silicon dioxide layer may be deposited using a CVD process. The silicon dioxide may be derived from tetraethyl orthosilicate (TEOS).

In one implementation, the oxide layer 120 is deposited using a low temperature CVD process (e.g., temperature in the range of about 250 to about 300 degrees Celsius). In one implementation, the oxide layer 120 can be deposited by PVD with a low bias.

At operation 230, a portion of the oxide layer 120 is removed from the bottom surface 110 of the feature 102 to expose the substrate 100 as depicted in FIG. 1C. During operation 230, a portion of the oxide layer 120 may be removed from the field region 105 to expose the oxide layer 112. The oxide layer 120 may be removed from the bottom surface 110 and the field region 105 using an etching process, for example, a reactive ion etching process or a sputtering etching process. In some implementations, the exposed surfaces of the oxide layer 120 may be directionally etched to remove the oxide layer 120 from the bottom surface 110 of feature 102 exposing the silicon material of the substrate 100. The oxide layer 112 on the field region 105 of the substrate 100 may be thinned or completely removed during the directional etching process.

The arrows 124′ represent the direction of gas ion movement, due to the generation of an electric field near the substrate surface of the substrate during processing, which causes the argon gas to collide with the top (planar) surface of the oxide layer 120 during the directional etch process. The arrows 124″ similarly show the direction of the gas ion movement at the bottom surface 110 of the feature 102. The oxide layer 120 along the at least one sidewall 108 may be thinned but is substantially unaffected by the etch process and so the oxide layer 120 deposited over the at least one sidewall 108 remains intact after the etch process is completed. Although the oxide layer 120 on the at least one sidewall 108 may be thinned during operation 230 it is not removed. Although the remaining thinned oxide layer 120 may provide a conductive path, the resistance of the thinned oxide layer 120 is typically very high and as a result, there won't be a significant amount of plating on the field region 105 and/or the at least one sidewall 108, thus providing for bottom-up fill. The oxide layer 120 along the at least one sidewall 108 and field region 105 prevents copper or nickel plating on the at least one sidewall 108 and field region 105. Plating takes place at the bottom 110 of the feature 102 where a metal seed layer 130 is formed.

In implementations where the etching process is a sputter etching process, the process may be an argon-based sputter etching process with a high bias, which is directional and etches mostly the oxide from the field region 105 and the oxide from the bottom surface 110. In some implementations, any remaining oxide on the bottom surface 110 after the etch process may be removed by a wet etch process. The wet etch process may be performed using a wet etch solution including 2% H₂O₂+3% hydrofluoric acid in 80% acetic acid solution (15% DI water).

At operation 240, the metal seed layer 130 is deposited on the exposed silicon at the bottom surface 110 of the feature 102 as depicted in FIG. 1D. The metal seed layer 130 may be deposited on the bottom surface 110 using a physical vapor deposition (PVD), chemical vapor deposition (CVD), electroplating deposition, electroless deposition or atomic layer deposition (ALD) deposition processes. In some implementations, the metal seed layer 130 deposition process may be conducted in the same deposition chamber as the barrier layer deposition process, described below. In some implementations, the metal seed layer 130 may be a copper (Cu) layer, a ruthenium (Ru) layer, a palladium (Pd) layer, a nickel (Ni) layer, a cobalt (Co) layer, or a layer that is an alloy containing one or more of these elements. In some implementations, the metal seed layer 130 is in the range of about 10 nm to about 250 nm thick. In some implementations, the metal seed layer 130 is in the range of about 100 nm to about 200 nm thick.

In some implementations, where the metal seed layer 130 is a nickel layer, the nickel layer may be deposited using an electroless plating process. Preparation of the silicon surface may include at least one of a hydrofluoric acid etch and an SC-1 dip to re-grow chemical oxide which is believed to produce better adhesion. The electroless nickel plating solution may comprise a nickel source (e.g., NiSO₄), a reducing agent (e.g., NH₄OH), and DI water. The reducing agent helps maintain a pH greater than 8 of the electroless nickel plating solution. The exposed silicon at the bottom 110 of the feature 102 functions as a reducing agent. The electroless plating solution may have pH from about 5 to about 6. The electroless nickel deposition process may be performed at a temperature of 95 degrees Celsius or greater with optional agitation such as impalement stirring or sonication.

In one implementation, the electroless nickel-plating process is a nickel displacement process. In one implementation, the electroless nickel plating solution includes adding 0.5 M NiSO₄ to 100 ml of water and heat the mixture to greater than 90 degrees Celsius. Then 200 ml of 30% NH₄OH is added to the mixture. The temperature of the mixture is maintained at 70 degrees Celsius. The substrate 100 is immersed in the plating solution for approximately 20 minutes followed by DI water rinsing and N₂ drying.

At operation 250, optionally, the metal seed layer 130 may be annealed to form a metal silicide layer (not shown) at the bottom surface 110 of the feature 102. The metal silicide layer comprises at least a portion of the metal seed layer 130 and at least a portion of the silicon containing substrate 100. Exemplary annealing processes include thermal annealing processes (e.g., RTP), laser annealing processes, such as millisecond annealing processes, nanosecond annealing processes, microsecond annealing processes, and flash lamp annealing processes. The metal silicide layer may be formed by annealing at a temperature within a range from about 400 degrees Celsius to less than 1,200 degrees Celsius. The metal silicide layer may be formed by annealing at a temperature within a range from about 700 degrees Celsius to less than 1,000 degrees Celsius.

At operation 260, optionally, to prevent copper diffusion into the substrate 100, a barrier layer 140 may be formed in the feature 102 on the remaining oxide layer 120, as depicted in FIG. 1G. The barrier layer 140 may be a conformal layer or a non-conformal layer. The barrier layer 140 may be formed using a suitable deposition process including atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD) or combinations thereof. A conformal barrier layer may be formed by an ALD or CVD process. A non-conformal barrier layer may be formed by a PVD process. In one implementation, the barrier layer 140 can be deposited by a PVD process with a low bias. In one implementation, the barrier layer 140 may be formed by a chamber of a cluster tool. In one implementation, the substrate 100 may be placed into a plasma enhanced ALD (PE-ALD), a plasma enhanced CVD (PE-CVD) or high density plasma CVD (HDP-CVD) chamber, such as the ULTIMA HDP-CVD™, Centura iSprint™ or Endura iLB™ systems, available from Applied Materials Inc., located in Santa Clara, Calif.

In one implementation, the barrier layer 140 may formed using a physical vapor deposition (PVD), chemical vapor deposition (CVD) or atomic layer deposition (ALD) deposition process. The barrier layer 140 may be a single deposited layer, or multiple deposited layers, containing ruthenium (Ru), titanium (Ti), titanium nitride (TiN), tungsten (W), tungsten nitride (WN), tungsten silicon nitride (WSiN), tantalum (Ta), tantalum nitride (TaN) or other alloy containing these materials. In some implementations, the single deposited layer or multiple deposited layer stack may contain an oxide layer. In some implementations, the oxide layer may be oxide layer 120. The oxide layer may be a silicon oxide or a silicon dioxide containing layer. The silicon oxide or silicon dioxide layer may serve as an insulating layer. The silicon oxide or silicon dioxide layer may be deposited using a CVD process. In one implementation, the multiple deposited layer stack may have a first layer that contains silicon dioxide and a second layer that contains TiN. The silicon dioxide may be derived from tetraethyl orthosilicate (TEOS). In some implementations, the barrier layer 140 may be from about 500 Å to about 2,000 Å thick (e.g., from about 1,000 Å to about 1,500 Å; from about 1,000 Å to about 2,000 Å.

In some implementations where the oxide layer 112 is present, the barrier layer 140 is deposited over the oxide layer 112. In some implementations where the oxide layer 112 is not present, the barrier layer 140 is deposited directly on the field region 105.

At operation 270, bottom-up filling of the feature 102 with a metal layer 150 by an electroplating process is performed by flowing current through the backside 106 of the substrate 100, as depicted in FIG. 1F and FIG. 1H. In some implementations, the feature 102 is preferentially filled from the metal seed layer 130 at the bottom of the feature 102 until the layer is about level with the field region 105 (e.g., bottom-up fill). In some implementations, the metal layer 150 may be a copper (Cu) layer, a cobalt (Co) layer, a nickel (Ni) layer, a silver (Ag) layer or a layer that is an alloy containing one or more of these elements. In some implementations, the feature 102 is filed using a multilayer fill process in which two or more layers are sequentially deposited to fill the feature 102. An exemplary bottom-up fill electroplating process is described below with reference to FIG. 3 and FIG. 4. In general, the metal layer 150 may be deposited using an electroplating deposition solution that contains one or more metal ion sources that allows the deposition of a layer that contains one or more metals. In one implementation, one of the metals ions is a copper ion and the other metal ion(s) are a metal selected from a group consisting of aluminum (Al), indium (In), molybdenum (Mo), tungsten (W), manganese (Mn), cobalt (Co), tin (Sn), nickel (Ni), magnesium (Mg), rhenium (Rh), beryllium (Be), phosphorus (P), boron (B), gallium (Ga), or ruthenium (Ru). In some implementations, a current of from about 0.5 Amps to 2 Amps is used. In some implementations, the deposition bias generally has a current density of from about 0.0005 A/cm² to about 0.01 A/cm² or less.

In some implementations of the processing sequence 200, the oxide layer 112 may be removed from the field region 105 by use of a material removal process, such as an electrochemical process or chemical mechanical polishing process (CMP). In some implementations, the oxide layer 120 may be removed from the field region 105 during the process of operation 230. In some implementations, this process operation includes the process of removing any over plating leftover after performing the deposition of the metal layer 150. The substrate 100 may also be exposed to a cleaning process to remove any plating solution and or wet contact solution. The cleaning process may comprise at least one of a spine, a rinse, and a dry.

FIG. 3 illustrates a schematic cross-sectional view of a plating cell 300 that may be used to perform the deposition processes described herein. FIG. 4 illustrates another schematic cross-sectional view of a plating cell 300 that may be used to perform the deposition processes described herein. The plating cell 300 of FIG. 3 and the plating cell 300 of FIG. 4 are identical except for the wet contact solutions used. It should also be understood that the wet contact solutions depicted in FIG. 3 and FIG. 4 are exemplary. The plating cell 300 comprises a wet contact solution compartment 310 and a plating solution compartment 320 with the substrate 100 positioned therebetween. Although the plating cell 300 is depicted in FIG. 3 as having a vertical orientation (i.e., the substrate has a vertically orientation), it should also be understood that the plating cell 300 may have a horizontal orientation with the wet contact solution compartment 310 positioned under the plating solution compartment 320.

A soluble anode 330 is positioned within the plating solution compartment 320. The soluble anode 330 typically comprises the material to be plated on the substrate 100. For example, in some implementations where copper is plated on the substrate 100, the soluble anode 330 comprises copper and supplies copper ions to the plating solution in the plating solution compartment 320.

An insoluble electrode 340 is positioned within the wet contact solution compartment. The insoluble electrode 340 typically comprises a material that is inert relative to the process chemistry in the wet contact solution compartment. In some implementations, the insoluble electrode 340 comprises boron doped carbon (BDC).

The plating cell 300 may be coupled to a power source 360 for supplying power to the various components of the plating cell 300. The power source 360 may be an RF or DC source. The power source 360 may be coupled with a controller 370. The controller 370 may be coupled with the plating cell 300 to control operation of the plating cell 300. The controller 370 may include one or more microprocessors, microcomputers, microcontrollers, dedicated hardware or logic, and a combination of the same.

The plating solution compartment 320 may be coupled with a first fluid supply 364 for supplying a pre-mixed plating solution or the precursors for forming the plating solution to the plating solution compartment 320. The wet contact solution compartment 310 may be coupled with a second fluid supply 366 for supplying the wet contact solution and any additional additives to the wet contact solution compartment 310.

In some implementations, the wet contact solution comprises a conductive solution capable of delivering current to the backside 106 of the substrate 100. In some implementations, the wet contact solution comprises an electrolyte. In some implementations, the wet contact solution comprises a conductive acid. It is believed that the conductive acid removes silicon from the backside 106 of the substrate 100 and provides current flow between the wafer and the electrode. One exemplary conductive acid is hydrofluoric acid. Hydrofluoric acid may be from about 10% (w/w) aqueous solution to about 49% (w/w) aqueous solution. The wet contact solution may comprise additional salts in order to increase the conductivity of the solution. Exemplary additional salts include potassium fluoride. In one implementation, the wet contact solution comprises a hydrofluoric acid solution, aqueous, (49%) and potassium fluoride.

In some implementations, the wet contact solution comprises a conductive base. In some implementations, the conductive base is potassium hydroxide (KOH). Conductive bases such as KOH typically do not cause porous silicon formation and exhibit low etch rates (46 Å/min) for silicon of 111 crystal orientation. Conductive bases such as KOH can also etch SiO₂ at elevated temperature at ˜15 A/min sufficient to provide wet contact. Experimental results confirmed improved plating current stability as function of time with a KOH based wet contact solution. It is believed that use of a conductive base (e.g., KOH) prevents plating current loss that may occur due to formation of porous silicon on the backside 106 of the substrate 100 when conductive acids are used.

Plating Solution:

In one implementation, the plating solution contains a metal ion source and at least one or more acid solutions. In some implementations, the plating solution is an electroplating solution. In other implementations, the plating solution is an electroless plating solution. Suitable acid solutions include, for example, inorganic acids such as sulfuric acid, phosphoric acid, pyrophosphoric acid, hydrochloric acid, perchloric acid, acetic acid, citric acid, combinations thereof, as well as acid electrolyte derivatives, including ammonium and potassium salts thereof.

In some implementations, the metal ion source within the plating solution is a copper ion source. Useful copper sources include copper sulfate (CuSO₄), copper (I) sulfide (Cu₂S), copper (II) sulfide (CuS), copper (I) chloride (CuCl), copper (II) chloride (CuCl₂), copper acetate (Cu(CO₂CH₃)₂), copper pyrophosphate (Cu₂P₂O₇), copper fluoroborate (Cu(BF₄)₂), copper acetate ((CH₃CO₂)₂Cu), copper acetylacetonate ((C₅H₇O₂)₂Cu), copper phosphates, copper nitrates, copper carbonates, copper sulfamate, copper sulfonate, copper pyrophosphate, copper cyanide, derivatives thereof, hydrates thereof or combinations thereof. Some copper sources are commonly available as hydrate derivatives, such as CuSO₄5H₂O, CuCl₂2H₂O and (CH₃CO₂)₂CuH₂O. The electrolyte composition can also be based on the alkaline copper plating baths (e.g., cyanide, glycerin, ammonia, etc.) as well. In one implementation, the concentration of copper ions in the electrolyte may range from about 0.1 M to about 1.1M. In one implementation, the concentration of copper ions in the electrolyte may range from about 0.4 M to about 0.9 M.

In one implementation, the plating solution is an additive-free plating solution. In one implementation, the additive-free plating solution contains copper-sulfate only.

Optionally, the plating solution may include one or more additive compounds. In some implementations, the plating solution contains an oxidizer. As used herein, an oxidizer may be used to oxidize a metal layer to a corresponding oxide, for example, copper to copper oxide. Examples of suitable oxidizers include peroxy compounds, e.g., compounds that may disassociate through hydroxyl radicals, such as hydrogen peroxide and its adducts including urea hydrogen peroxide, percarbonates, and organic peroxides including, for example, alkyl peroxides, cyclical or aryl peroxides, benzoyl peroxide, peracetic acid, and di-t-butyl peroxide. Sulfates and sulfate derivatives, such as monopersulfates and dipersulfates may also be used including for example, ammonium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, and potassium persulfate. Salts of peroxy compounds, such as sodium percarbonate and sodium peroxide may also be used. In some implementations, the oxidizer can be present in the plating solution in an amount ranging between about 0.001% and about 90% by volume or weight. In another implementation, the oxidizer can be present in the plating solution in an amount ranging between about 0.01% and about 20% by volume or weight. In yet another implementation, the oxidizer can be present in the plating solution in an amount ranging between about 0.1% and about 15% by volume or weight.

In some implementations, it is desirable to add a low cost pH adjusting agent, such as potassium hydroxide (KOH) or sodium hydroxide (NaOH) to form an inexpensive electrolyte that has a desirable pH to reduce the cost of ownership to form an energy device. In some implementations, it is desirable to use tetramethylammonium hydroxide (TMAH) to adjust the pH.

In some implementations, it may be desirable to add a second metal ion to the primary metal ion containing electrolyte bath (e.g., copper ion containing bath) that will plate out or be incorporated in the growing electrochemically deposited layer or on the grain boundaries of the electrochemically deposited layer. The formation of a metal layer that contains a percentage of a second element can be useful to reduce the intrinsic stress of the formed layer and/or improve its electrical and electromigration properties. In one implementation, the metal ion source within the electrolyte solution is an ion source selected from a group comprising silver, tin, zinc, cobalt, nickel ion sources, and combinations thereof. In one implementation, the concentration of silver (Ag), tin (Sn), zinc (Zn), cobalt (Co), or nickel (Ni) ions in the electrolyte may range from about 0.1 M to about 0.4M.

Examples of suitable nickel sources include nickel sulfate, nickel chloride, nickel acetate, nickel phosphate, derivatives thereof, hydrates thereof or combinations thereof.

Examples of suitable tin sources include soluble tin compounds. A soluble tin compound can be a stannic or stannous salt. The stannic or stannous salt can be a sulfate, an alkane sulfonate, or an alkanol sulfonate. For example, the bath soluble tin compound can be one or more stannous alkane sulfonates of the formula: (RSO₃)₂Sn where R is an alkyl group that includes from one to twelve carbon atoms. The stannous alkane sulfonate can be stannous methane sulfonate with the formula:

and the bath soluble tin compound can also be stannous sulfate of the formula: SnSO₄.

Examples of the soluble tin compound can also include tin(II) salts of organic sulfonic acid such as methanesulfonic acid, ethanesulfonic acid, 2-propanolsulfonic acid, p-phenolsulfonic acid and like, tin(II) borofluoride, tin(II) sulfosuccinate, tin(II) sulfate, tin(II) oxide, tin(II) chloride and the like. These soluble tin(II) compounds may be used alone or in combination of two or more kinds.

Example of suitable cobalt sources may include cobalt salts selected from cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt bromide, cobalt carbonate, cobalt acetate, ethylenediaminetetraacetic acid cobalt, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, glycine cobalt (III), cobalt pyrophosphate, and combinations thereof.

The plating solution may also contain manganese or iron at a concentration within a range from about 20 ppm to about 600 ppm. In another implementation, the plating solution may contain manganese or iron at a concentration within a range from about 100 ppm to about 400 ppm. Possible iron sources include iron(II) chloride (FeCl₂) including hydrates, iron (III) chloride (FeCl₃), iron (II) oxide (FeO), Iron (II, III) oxide (Fe₃O₄), and Iron (III) oxide (Fe₂O₃). Possible manganese sources include manganese (IV) oxide (MnO₂), manganese (II) sulfate monohydrate (MnSO₄.H₂O), manganese (II) chloride (MnCl₂), manganese (III) chloride (MnCl₃), manganese fluoride (MnF₄), and manganese phosphate (Mn₃(PO₄)₂).

In some implementations, the plating solution contains free copper ions in place of copper source compounds and complexed copper ions.

In some implementations, the plating solution may also comprise at least one complexing agent or chelator to form complexes with the copper ions while providing stability and control during the deposition process. Complexing agents also provide buffering characteristics for the electroless copper solution. Complexing agents generally have functional groups, such as carboxylic acids, dicarboxylic acids, polycarboxylic acids, amino acids, amines, diamines or polyamines. Specific examples of useful complexing agents for the electroless copper solution include ethylenediaminetetraacetic acid (EDTA), ethylene diamine (EDA), citric acid, citrates, glyoxylates, glycine, amino acids, derivatives thereof, salts thereof or combinations thereof. In one implementation, the plating solution may have a complexing agent at a concentration within a range from about 50 mM to about 500 mM. In another implementation, the plating solution may have a complexing agent at a concentration within a range from about 75 mM to about 400 mM. In yet another implementation, the plating solution may have a complexing agent at a concentration within a range from about 100 mM to about 300 mM, such as about 200 mM. In one implementation, an EDTA source is used as the complexing agent within the plating solution. In one example, the plating solution contains about 205 mM of an EDTA source. The EDTA source may include EDTA, ethylenediaminetetraacetate, salts thereof, derivatives thereof or combinations thereof.

In certain implementations, the plating solution contains at least one reductant. Reductants provide electrons to induce the chemical reduction of copper ions while forming and depositing the copper material, as described herein. Reductants include organic reductants (e.g., glyoxylic acid or formaldehyde), hydrazine, organic hydrazines (e.g., methyl hydrazine), hypophosphite sources (e.g., hypophosphorous acid (H₃PO₂), ammonium hypophosphite ((NH₄)_(4−x)H_(x)PO₂) or salts thereof), borane sources (e.g., dimethylamine borane complex ((CH₃)₂NHBH₃), DMAB), trimethylamine borane complex ((CH₃)₃NBH₃), TMAB), tert-butylamine borane complex (tBuNH₂BH₃), tetrahydrofuran borane complex (THFBH₃), pyridine borane complex (C₅H₅NBH₃), ammonia borane complex (NH₃BH₃), borane (BH₃), diborane (B₂H₆), derivatives thereof, complexes thereof, hydrates thereof or combinations thereof. In one implementation, the plating solution may have a reductant at a concentration within a range from about 20 mM to about 500 mM. In another implementations, the plating solution may have a reductant at a concentration within a range from about 100 mM to about 400 mM. In yet another implementations, the plating solution may have a reductant at a concentration within a range from about 150 mM to about 300 mM, such as about 220 mM. Preferably, an organic reductant or organic-containing reductant is utilized within the plating solution, such as glyoxylic acid or a glyoxylic acid source. The glyoxylic acid source may include glyoxylic acid, glyoxylates, salts thereof, complexes thereof, derivatives thereof or combinations thereof. In one example, glyoxylic acid monohydrate (HCOCO₂H.H₂O) is contained within the electroless copper solution at a concentration of about 217 mM.

The plating solution may contain other additives, which may be, for example, levelers, inhibitors, suppressors, brighteners, accelerators, or other additives known in the art, are typically organic materials that adsorb onto the surface of the substrate being plated. Useful suppressors typically include polyethers, such as polyethylene, glycol, or other polymers, such as polypropylene oxides, which adsorb on the substrate surface, slowing down copper deposition in the adsorbed areas. Useful accelerators typically include sulfides or disulfides, such as bis(3-sulfopropyl) disulfide, which compete with suppressors for adsorption sites, accelerating copper deposition in adsorbed areas. Useful inhibitors typically include sodium benzoate and sodium sulfite, which inhibit the rate of copper deposition on the substrate. During plating, the additives are consumed at the substrate surface, but are being constantly replenished by the electroplating solution. However, differences in diffusion rates of the various additives result in different surface concentrations at the top and the bottom of the features, thus setting up different plating rates in the features. Ideally, these plating rates should be higher at the bottom of the feature for bottom-up fill. Thus, an appropriate composition of additives in the plating solution is may be used to achieve a void-free fill of the features.

The plating solution may also have a surfactant. The surfactant acts as a wetting agent to reduce the surface tension between the copper containing solution and the substrate surface. In one implementation, the plating solution generally contains a surfactant at a concentration of about 1,000 ppm or less. In another implementation, the plating solution generally contains a surfactant at a concentration of about 500 ppm or less, such as within a range from about 100 ppm to about 300 ppm. The surfactant may have ionic or non-ionic characteristics. Exemplary surfactants include glycol ether based surfactants, such as polyethylene glycol (PEG), polypropylene glycol (PPG) or the like. Due to beneficial characteristics, PEG and PPG may be used as a surfactant, an inhibitor and/or a suppressor. In one example, a glycol ether based surfactant may contain polyoxyethylene units, such as TRITON® 100, available from The Dow Chemical Company. Other surfactants that may be used within the electroless copper solution include dodecyl sulfates, such as sodium dodecyl sulfate (SDS). The surfactants may be single compounds or a mixture of compounds having molecules that contain varying lengths of hydrocarbon chains.

The balance or remainder of the plating solution described above may be a solvent, such as a polar solvent, including water, such as deionized water, and organic solvents, for example, alcohols or glycols.

In one implementation, the plating solution comprises 220 g/L of CuSO₄, 27 ml/L of H₂SO₄, a drop of HCl, and the remainder DI water to 1 L.

EXAMPLE

The following non-limiting example further illustrates implementations described herein. However, the example is not intended to be all inclusive and is not intended to limit the scope of the implementations described herein.

Example 1

A silicon coupon measuring 8×8 cm was exposed to an electroless nickel plating solution. The nickel plating solution was formed by adding 0.5 M NiSO₄ to 100 ml of water and heating the mixture to greater than 90 degrees Celsius. Then 200 ml of 30% NH₄OH was added to the mixture. The temperature of the mixture was maintained at 70 degrees Celsius. The substrate 100 was immersed in the electroless plating solution for approximately 20 minutes followed by DI water rinsing and N₂ drying.

The silicon coupon measuring was positioned in a plating cell similar to the plating cell 300 in FIG. 3. A front side of the silicon coupon was exposed to a plating solution comprising 220 g/L of CuSO₄, 27 ml/L of H₂SO₄, a drop of HCl, and the remainder DI water to 1 L. The backside of the silicon coupon was exposed to a wet contact solution comprising a hydrofluoric acid solution, aqueous, (49%) and potassium fluoride. An electric current density of 0.005 ampere per square centimeter (A/cm²) and a potential of between 1.24 to 1.3 volts was applied for a period of approximately four minutes. A thin copper layer was deposited on the silicon coupon successfully demonstrating that copper could be plated on silicon using a wet backside contact.

In summary some of the benefits of some implementations of the present disclosure provide methods for filling a feature with a conductive contact material, such that the contact material is deposited free of voids, seams, and other defects. The improved methods described herein are especially advantageous for filling high aspect ratio features. Implementations described herein are especially advantageous in through-silicon via (TSV) applications. In some implementations, defect free deposition is achieved by bottom-up plating with a simple copper containing chemistry with minimum additives in order to maximize the copper plating rate. In some implementations described herein, methods for bottom-up via plating using wet wafer backside contact are used to achieve conformal copper deposition at high plating rates. As used herein “substrate” may be a support substrate with or without layers formed thereon. The patterned substrate may be an insulator or a semiconductor of a variety of doping concentrations and profiles and may be, for example, a semiconductor substrate of the type used in the manufacture of integrated circuits. Exposed “silicon” of the patterned substrate is predominantly Si but may include minority concentrations of other elemental constituents such as nitrogen, oxygen, hydrogen, carbon and the like. Exposed “silicon nitride” of the patterned substrate is predominantly Si₃N₄ but may include minority concentrations of other elemental constituents such as oxygen, hydrogen, carbon and the like. Exposed “silicon oxide” of the patterned substrate is predominantly SiO₂ but may include minority concentrations of other elemental constituents such as nitrogen, hydrogen, carbon and the like.

Having disclosed several implementations, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the disclosed implementations. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present disclosure. Accordingly, the above description should not be taken as limiting the scope of the disclosure.

When introducing elements of the present disclosure or exemplary aspects or implementation(s) thereof, the articles “a,” “an,” “the” and “said” are intended to mean that there are one or more of the elements.

The terms “comprising,” “including” and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements.

All amounts, ratios, proportions and other measurements are by weight unless stated otherwise. All percentages refer to weight percent based on total composition according to the practice of the present disclosure unless stated otherwise.

While the foregoing is directed to implementations of the present disclosure, other and further implementations of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. 

The invention claimed is:
 1. A method for depositing a material on a substrate, comprising: depositing a conformal oxide layer over at least one sidewall and a bottom surface of a feature formed in a silicon substrate, wherein the silicon substrate comprises: a field region surrounding the feature; and a backside, wherein the feature extends from the field region toward the backside; selectively removing a portion of the conformal oxide layer from the bottom surface of the feature to expose a portion of the silicon substrate; depositing a metal seed layer on the exposed portion of the silicon substrate at the bottom surface of the feature; forming a conformal barrier layer on the conformal oxide layer after depositing the metal seed layer on the exposed portion of the silicon substrate; and exposing the silicon substrate to an electroplating process by flowing a current through the backside of the silicon substrate to form a metal layer on the metal seed layer.
 2. The method of claim 1, wherein the exposing the silicon substrate to an electroplating process by flowing a current through the backside of the silicon substrate to form a metal layer on the metal seed layer comprises exposing the backside of the silicon substrate to a wet contact solution comprising a hydrofluoric acid solution and exposing the metal seed layer to a copper containing solution.
 3. The method of claim 2, wherein the wet contact solution further comprises potassium fluoride.
 4. The method of claim 1, wherein the conformal barrier layer comprises titanium nitride (TiN), tungsten nitride (WN), or tungsten-silicon nitride (WSiN).
 5. The method of claim 4, wherein the conformal oxide layer is a silicon dioxide layer.
 6. The method of claim 1, wherein the metal of the metal seed layer is selected from cobalt and nickel.
 7. The method of claim 6, wherein the metal of the metal seed layer is nickel deposited by an electroless process.
 8. The method of claim 6, wherein the metal of the metal seed layer is cobalt deposited by either an electroless process or a chemical vapor deposition process.
 9. The method of claim 1, wherein the metal layer comprises copper.
 10. The method of claim 1, wherein the feature is an aperture selected from contacts, vias, and lines.
 11. The method of claim 1, wherein the exposing the silicon substrate to an electroplating process by flowing a current through a backside of the silicon substrate to form a metal layer on the metal seed layer comprises exposing the backside of the silicon substrate to a potassium hydroxide solution and exposing the metal seed layer to a copper containing solution.
 12. A method for depositing a material on a substrate, comprising: depositing an oxide layer over at least one sidewall and a bottom surface of a feature formed in a silicon substrate, wherein the silicon substrate comprises: a field region surrounding the feature and having an oxide layer disposed thereon; and a backside, wherein the feature extends from the field region toward the backside; selectively removing a portion of the oxide layer from the bottom surface of the feature to expose a portion of the silicon substrate, wherein at least a portion of the oxide layer remains on the at least one sidewall; depositing a metal seed layer on the exposed portion of the silicon substrate at the bottom surface of the feature; forming a barrier layer on the portion of the oxide layer remaining on the at least one sidewall, wherein the barrier layer comprises titanium nitride (TiN), tungsten nitride (WN), or tungsten-silicon nitride (WSiN); and exposing the silicon substrate to an electroplating process, comprising: exposing the backside of the silicon substrate to a potassium hydroxide solution and exposing the seed layer to a copper containing solution; and flowing a current through the backside of the silicon substrate to form a metal layer on the metal seed layer.
 13. The method of claim 12, wherein the metal of the metal seed layer is nickel deposited by an electroless process.
 14. The method of claim 13, wherein the metal layer comprises copper.
 15. The method of claim 12, wherein the feature is an aperture selected from contacts, vias, and lines.
 16. A method for depositing a material on a substrate, comprising: depositing an oxide layer over at least one sidewall and a bottom surface of a feature formed in a silicon substrate, wherein the silicon substrate comprises: a field region surrounding the feature and having an oxide layer disposed thereon; and a backside, wherein the feature extends from the field region toward the backside; selectively removing a portion of the oxide layer from the bottom surface of the feature to expose a portion of the silicon substrate, wherein selectively removing a portion of the oxide layer comprises exposing the oxide layer to an argon-based sputter etching process followed by a wet etch process, and at least a portion of the oxide layer remains on the at least one sidewall; depositing a metal seed layer on the exposed portion of the silicon substrate at the bottom surface of the feature; forming a barrier layer on the portion of the oxide layer remaining on the at least one sidewall; and exposing the silicon substrate to an electroplating process by flowing a current through the backside of the silicon substrate to form a metal layer on the metal seed layer.
 17. A method for depositing a material on a substrate, comprising: depositing a conformal oxide layer over at least one sidewall and a bottom surface of a feature formed in a silicon substrate, wherein the silicon substrate comprises: a field region surrounding the feature; and a backside, wherein the feature extends from the field region toward the backside; selectively removing a portion of the conformal oxide layer from the bottom surface of the feature to expose a portion of the silicon substrate; depositing a metal seed layer on the exposed portion of the silicon substrate at the bottom surface of the feature; and exposing the silicon substrate to an electroplating process, comprising: exposing the backside of the silicon substrate to a wet contact solution comprising a hydrofluoric acid solution and potassium fluoride; exposing the seed layer to a copper containing solution; and flowing a current through the backside of the silicon substrate to form a metal layer on the metal seed layer.
 18. The method of claim 17, wherein the metal layer comprises copper and the metal of the metal seed layer is selected from cobalt and nickel.
 19. A method for depositing a material on a substrate, comprising: depositing a conformal oxide layer over at least one sidewall and a bottom surface of a feature formed in a silicon substrate, wherein the silicon substrate comprises: a field region surrounding the feature; and a backside, wherein the feature extends from the field region toward the backside; selectively removing a portion of the conformal oxide layer from the bottom surface of the feature to expose a portion of the silicon substrate; depositing a metal seed layer on the exposed portion of the silicon substrate at the bottom surface of the feature; forming a conformal barrier layer on the oxide layer after depositing the metal seed layer on the exposed silicon substrate; and exposing the silicon substrate to an electroplating process, comprising: exposing the backside of the silicon substrate to a potassium hydroxide solution; exposing the metal seed layer to a copper containing solution; and flowing a current through the backside of the silicon substrate to form a metal layer on the metal seed layer.
 20. The method of claim 19, wherein the metal layer comprises copper and the metal of the metal seed layer is selected from cobalt and nickel. 